EP0072573A2 - Process for producing pitch for use as raw material for carbon fibers and carbon fibers produced from the pitch - Google Patents
Process for producing pitch for use as raw material for carbon fibers and carbon fibers produced from the pitch Download PDFInfo
- Publication number
- EP0072573A2 EP0072573A2 EP82107538A EP82107538A EP0072573A2 EP 0072573 A2 EP0072573 A2 EP 0072573A2 EP 82107538 A EP82107538 A EP 82107538A EP 82107538 A EP82107538 A EP 82107538A EP 0072573 A2 EP0072573 A2 EP 0072573A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pitch
- oil
- producing
- carbon fibers
- boiling point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 34
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 title claims description 27
- 238000009835 boiling Methods 0.000 claims abstract description 30
- 238000004821 distillation Methods 0.000 claims abstract description 26
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 19
- 239000003208 petroleum Substances 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 54
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000010779 crude oil Substances 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 4
- 239000011295 pitch Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- 238000002074 melt spinning Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
Abstract
Description
- The present invention relates to a process for producing pitch (which is a raw material for producing carbon fibers) using a petroleum heavy residual oil, and carbon fibers produced from the pitch.
- In pitches which are used as a raw material for producing carbon fibers having excellent strength and excellent modulus of elasticity, optical anisotropy can be observed by a polarizing microscope. More specifically, such pitches are believed to contain a mesophase as described in U.S. Patent 3,974,264. Further, it has recently been disclosed in Japanese Patent Application (OPI) 160427/79 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") that carbon fibers having a high modulus of elasticity can be produced with a pitch containing a neo-mesophase. By heating such pitches for a short time optical anisotropy is observed in them. Further, pitches used as a raw material for carbon fibers need not possess only optical anisotropy but must also be capable of being stably spun. However, it is not easy to produce pitches having both properties. In order to produce carbon fibers having excellent strength and excellent modulus of elasticity, it is not always possible to use any material as the raw material for making pitches. Materials having specified properties have been required.
- It should be noted that in many published patents, for example, as described in U.S. Patents 3,976,729 and 4,026,788, the raw material is not specified in the patent claims. Furthermore, such patents indicate that pitches used as a raw material for carbon fibers can be produced only by carrying out thermal modification of a wide variety of raw materials. However, according to the detailed descriptions and examples in such patents, the desired pitches can only be produced by using specified raw materials.
- For example, U.S. Patent 4,115,527 discloses that substances such as chrysene, etc. or tarry materials obtained as by-products in high.temperature cracking of petroleum crude oil are suitable for producing the pitch, i.e., a carbon fiber precursor, but conventional petroleum asphalts and coal tar pitches are not suitable. Further, U.S. Patent 3,974,264 discloses that an aromatic base carbonaceous pitch having a carbon content of about 92 to about 96% by weight and a hydrogen content of about 4 to about 8% by weight is generally suitable for controlling a mesophase pitch. It has been described that elements other than carbon and hydrogen, such as oxygen, sulfur and nitrogen, should not be present in an amount of more than about 4% by weight, because they are not suitable. Further, Example 1 of the same patent publication discloses that the precursor pitch used has properties comprising a density of 1.23 g/cc, a softening point of 120°C, a quinoline insoluble content of 0.83% by weight, a carbon content of 93.0%, a hydrogen content of 5.6%, a sulfur content of 1.1% and an ash content of 0.044%. Even if a density of 1.23 g/cc in these properties is maintained, it should be noted that it is difficult to obtain conventional petroleum heavy oil having such a high density. Examples as described in the other U.S. Patents 3,976,729, 4,026,788 and 4,005,183 also disclose that the pitch is produced with a specified raw material.
- The properties of heavy petroleum oils depend essentially upon the properties of crude oils from which they were produced and the process for producing the heavy oil. However, generally, it is rare that heavy oils having the suitable properties described in the above-described Examples are produced, and, in many cases, they can not be obtained. Accordingly, in order to produce carbon fibers industrially in a stabilized state, which have excellent strength and excellent modulus of elasticity with petroleum heavy oils, it is necessary to develop a process for producing a pitch wherein the finally resulting pitch has properties which are always within a specified range even if the properties of the raw material for the pitch vary.
- An object of this invention is to provide a process for producing a pitch useful as raw material for producing carbon fibers having an excellent strength and a high modulus of elasticity.
- In accordance with one aspect of the invention, this object is achieved by a process for producing a pitch used as a raw material for carbon fibers characterised by carrying out hydrogenation treatment of a reduced pressure distillate oil prepared by reduced pressure distillation of a petroleum heavy residual oil, carrying out catalytic cracking of the resulting hydrogenated oil, distilling the resulting cracked oil to produce a high boiling point fraction having a boiling point of more than 300°C, and carrying out thermal modification thereof.
- According to another aspect of the invention, a pitch produced according to the method may be used for the manufacture of carbon fibers.
- According to a further aspect of the invention, there is provided carbon fibers produced from a pitch produced in accordance with the method.
- For a better understanding of the invention and to show how the same may be carried into effect, reference will now be made, purely for purposes of illustration, to a number of non-limiting examples of methods in accordance with the invention.
- Examples of petroleum heavy residual oils which may be used in the present invention include atmospheric pressure distillation residual oils and heavy residual oils from a thermal cracking process such as visbreak- ing, etc. The petroleum heavy residual oils having a boiling point of more than 300°C is preferred. The atmospheric pressure distillation residual oils are most commonly used.
- The above-described petroleum heavy residual oils can be processed by a reduced pressure distillation apparatus to obtain a distillate fraction. 95% or more of the distillate fraction has a boiling point of 300 - 550°C (atmospheric pressure). The resulting heavy fraction is subjected to hydrogenation treatment in the presence of a conventional hydrogenating catalyst (e.g., a catalyst containing the sulfides or oxides of such combination of metals as nickel-molybdenum, cobalt-molybdenum, etc.) at a temperature of 300 - 410°C, a pressure of 40 - 150 kg/cm2G, a liquid space velocity of 0.5 - 3.0 per hour, and a ratio of hydrogen/oil of 260 - 2,000 Nm3/Kl. By carrying out this treatment impurities such as sulfur, nitrogen or metals are removed from the reduced pressure distillate oil. The resulting hydrogenated oil preferably has a sulfur content of not more than 0.4% by weight.
- When producing carbon fibers having a high modulus of elasticity, it is necessary to remove sulfur in the pitch, because a high modulus of elasticity cannot be obtained if the sulfur content of the pitch is large. It is preferred to remove the sulfur prior to the final step, because it is difficult to remove sulfur from the pitch in the final step. It is also necessary to remove metals which form ash by carbonization. Such metals can cause deterioration of the strength or modulus of elasticity of carbon fibers.
- The above-described hydrogenated oil is subjected to a catalytic cracking reaction in the presence of a catalytic cracking catalyst comprising amorphous silica-alumina, silica-magnesia or zeolite catalysts. The catalytic cracking reaction is carried out at a temperature of 470 - 540°C, a pressure of 0.5 - 5.0 kg/cm2G and a ratio of catalyst/oil of 5 - 15 parts by weight. A high boiling point fraction having a boiling point of more than 300°C is obtained by distillation of the resulting cracking oil.
- The resulting high boiling point fraction is subjected to thermal modification at a temperature of 390 - 430°C for 1 - 30 hours, by which a pitch which can be used as a raw material for making carbon fibers having a high modulus of elasticity can be produced: In the residual heavy fraction after the catalytic cracking reaction, the difference in properties due to any disparity in the raw material becomes smaller due to the effects of the catalytic reaction together with the above-described hydrogenation treatment. Further, the residual heavy fraction develops a chemical composition comprising a large amount of aromatic compounds.
- The actual conditions required to obtain the best results in the above-described series of steps depend on the properties of the petroleum heavy residual oil which is used as a starting material as well as the properties of the pitch which will be used as a raw material for making carbon fibers as the final product. By carrying out a series of these steps any difference due to properties of the starting material becomes smaller. Therefore, by carrying out these steps, it is possible to keep the properties of the pitch which is used as a raw material for making carbon fibers within a specified range. Since the properties of the petroleum heavy residual oil (used as the starting material) are fairly different from others because of the crude oil, it is generally difficult to produce pitch (which can be successfully used to make carbon fibers having high strength and high modulus of elasticity and specified properties) by only carrying out the thermal modification of such petroleum heavy oil at 380°C to 450°C.
- However, a pitch which can be used as a raw material for carbon fibers having high modulus of elasticity can be produced industrially and stably with various kinds of petroleum heavy residual oils. The pitch is produced by carrying out a series of processings comprising reduced pressure distillation ) hydrogenation treatment e catalytic cracking ) distillation 7 thermal modification. By carrying out these steps it is possible to use a raw material which could not be used for producing a pitch for carbon fibers in accordance with prior processes.
- In the following, the present invention is illustrated in greater detail by further specific examples. However, this invention is not limited to these examples.
- An atmospheric pressure distillation residual oil of Middle East crude oil (A) was subjected to reduced pressure distillation to obtain a fraction having a boiling point of 300 - 550°C (an atmospheric pressure). The resulting reduced pressure distillation fraction was subjected to hydrogenation treatment in the presence of a cobalt-molybdenum catalyst. The hydrogenation was carried out at a temperature of 370°C, a pressure of 60 kg/cm2G, a liquid space velocity of 1.9 per hour and a ratio of hydrogen to oil of 360 Nm3Kl. The hydrogenated oil was subjected to a catalytic cracking reaction using a zeolite catalyst. The cracking was carried out at a temperature of 500°C, a pressure of 1.5 kg/cm 2 G and a catalyst/oil ratio of 9 parts by weight. The residual heavy oil obtained from the catalytic cracking reaction was distilled to obtain a high boiling point fraction having a boiling point of more than 300°C. The high boiling point fraction was subjected to thermal modification at a temperature of 410°C for 20 hours to obtain a pitch which could be used as a raw material for making carbon fibers.
- The properties of the atmospheric distillation residual oil of Middle East crude oil (A) used as a raw material, and the properties of the oil after hydrogenation treatment, as well as the properties of the high boiling point fraction after catalytic cracking and the properties of the resulting pitch are shown in the appended Table 1.
- Carbon fibers were obtained by melt spinning the above-described pitch at 360°C infusiblizing at 260°C in air and carbonizing at 1,000°C. The resulting carbon fibers had a tensile strength of 11 tons/cm2 and a modulus of elasticity of 1,300 tons/cm2. When carbonized fibers prepared by carbonizing at 1,000°C were additionally graphitized at 1,900°C, the resulting carbon fibers had a tensile strength of 15 tons/cm2 and a modulus of elasticity of 2,300 tons/cm .
- An atmospheric pressure distillation residual oil of Middle East crude oil (B) was subjected to reduced pressure distillation to obtain a fraction having a boiling point of 300 - 550°C (at atmospheric pressure). The resulting reduced pressure distillation fraction was subjected to hydrogenation treatment in the presence of a cobalt-molybdenum catalyst. The hydrogenation was carried out at a temperature of 380°C, a pressure of 60 kg/cm2, a liquid space velocity of 1.8 per hour and a ratio of hydrogen per oil of 400 Nm3/Kl. The hydrogenated oil was subjected to a catalytic cracking reaction with a zeolite catalyst. The cracking was carried out at a temperature of 500°C and a pressure of 1.5 Kg/cm2 and a catalyst/oil ratio of 9 parts by weight. The residual heavy oil obtained from the catalytic cracking reaction was distilled to obtain a high boiling point fraction having a boiling point of more than 300°C. The high boiling point fraction was subjected to heat treatment at a temperature of 420°C for 10 hours to obtain a pitch which could be used as a raw material for making carbon fibers.
- The properties of the atmospheric pressure distillation residual oil of Middle East crude oil (B) used as the raw material, and the properties of the oil after hydrogenation treatment, as well as the properties of the high boiling point fraction after catalytic cracking treatment and properties of the pitch are shown in the appended Table 1.
- An atmospheric pressure distillation residual oil of Middle East crude oil (A) was subjected to thermal modification at a temperature of 410°C for 18 hours. The properties of the atmospheric pressure distillation residual oil of Middle East crude oil (A) used as a raw material and the properties of the pitch are shown in the appended Table 1.
- Fibers were obtained by melt spinning the pitch at 350°C, infusiblizing in the air and carbonizing at 1,000°C. The fibers obtained had a tensile strength of 1.9 tons/cm2 and a modulus of elasticity of 140 tons/cm .
- An atmospheric pressure distillation residual oil of Middle East crude oil (A) was subjected to reduced pressure distillation to obtain a fraction having a boiling point in the range of 300 - 550°C. The resulting reduced pressure distillation fraction was subjected to thermal modification at a temperature of 410°C for 20 hours. The yield of the pitch obtained after the heat treatment was low and it was not possible to obtain the pitch in an amount necessary to examine its properties.
- An atmospheric pressure distillation residual oil of Middle East crude oil (A) was subjected to reduced pressure distillation to obtain a fraction having a boiling point in the range of 300 - 550°C (at atmospheric pressure). The resulting reduced pressure distillation fraction was subjected to a catalytic cracking reaction using a zeolite catalyst. The cracking was carried out at a temperature of 500°C, a pressure of 1.5 kg/cm2G and a catalyst/oil ratio of 9 parts by weight without the hydrogenation treatment. The residual heavy oil obtained by the catalytic cracking reaction was distilled to obtain a high boiling point fraction having a boiling point of more than 300°C. The high boiling point fraction was subjected to thermal modification at a temperature of 410°C for 20 hours to obtain a pitch.
- The properties of the atmospheric distillation residual oil of Middle East crude oil (A) used as a raw material, the properties of the high boiling point fraction after catalytic cracking as well as the properties of the resulting pitch are shown in the appended Table 1.
- The pitch obtained was subjected to melt spinning at about 365°C. However, the fiber obtained by the melt spinning broke frequently as compared with the pitch used as a raw material of Example 1. Accordingly, the melt spinning was very difficult to carry out. Further, the melt-spun fiber was infusiblized at 260°C in the air and then carbonized at 1,000°C. The resulting product had a tensile strength of 9 tons/cm2 and a modulus of elasticity of 1,010 ton/cm2. When the carbonized fibers prepared by carbonizing at 1,000°C were additionally graphitized at 1,900°C, they had a tensile strength of 10 tons/cm2 and a modulus of elasticity of 1,610 ton/cm2.
- Thus, there has been described a process for producing a pitch which can be used for producing carbon fibers having excellent properties industrially in a stabilized state, and making use of an easily available petroleum heavy residual oil.
-
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP128141/81 | 1981-08-18 | ||
JP56128141A JPS5829885A (en) | 1981-08-18 | 1981-08-18 | Preparation of pitch used as raw material for carbon fiber |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0072573A2 true EP0072573A2 (en) | 1983-02-23 |
EP0072573A3 EP0072573A3 (en) | 1983-04-13 |
EP0072573B1 EP0072573B1 (en) | 1986-08-06 |
Family
ID=14977407
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82107538A Expired EP0072573B1 (en) | 1981-08-18 | 1982-08-18 | Process for producing pitch for use as raw material for carbon fibers and carbon fibers produced from the pitch |
Country Status (4)
Country | Link |
---|---|
US (1) | US4462894A (en) |
EP (1) | EP0072573B1 (en) |
JP (1) | JPS5829885A (en) |
DE (1) | DE3272453D1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0084776A2 (en) * | 1982-01-13 | 1983-08-03 | Mitsubishi Oil Company, Limited | Process for producing pitch for using as raw material for carbon fibers |
EP0117099A2 (en) * | 1983-02-08 | 1984-08-29 | Fuji Standard Research Inc. | Novel carbonaceous pitch, process for the preparation thereof and use thereof to make carbon fibers |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645584A (en) * | 1981-09-24 | 1987-02-24 | Amoco Corporation | Mesophase pitch feedstock from hydrotreated decant oils |
JPS59196390A (en) * | 1983-04-22 | 1984-11-07 | Agency Of Ind Science & Technol | Preparation of pitch for carbon fiber |
JPS62277491A (en) * | 1986-05-26 | 1987-12-02 | Maruzen Petrochem Co Ltd | Production of meso-phase pitch |
JPS6383616U (en) * | 1986-11-19 | 1988-06-01 | ||
US6717021B2 (en) | 2000-06-13 | 2004-04-06 | Conocophillips Company | Solvating component and solvent system for mesophase pitch |
ES2254001B1 (en) * | 2004-08-10 | 2007-08-16 | Repsol Ypf, S.A. | PROCEDURE FOR OBTAINING BREAS AND USE OF THE SAME. |
TWI789017B (en) * | 2021-09-17 | 2023-01-01 | 明基材料股份有限公司 | High-haze anti-glare film and high-haze anti-glare anti-reflection film |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2992181A (en) * | 1957-09-11 | 1961-07-11 | Sinclair Refining Co | Process for producing a petroleum base pitch |
DE2006524A1 (en) * | 1969-02-13 | 1970-08-27 | Kureha Kagaku Kogyo Kabushiki Kaisha, Tokio | Process for rendering pitch parts infusible |
DE1966045A1 (en) * | 1968-04-04 | 1971-05-19 | Kureha Chemical Ind Co Ltd | Resinous pitch compositions |
US4086156A (en) * | 1974-12-13 | 1978-04-25 | Exxon Research & Engineering Co. | Pitch bonded carbon electrode |
FR2412606A1 (en) * | 1977-12-21 | 1979-07-20 | Standard Oil Co | PROCESS FOR CRACKING HEAVY HYDROCARBON CURRENTS |
Family Cites Families (27)
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BE534075A (en) * | 1953-12-14 | |||
US2932611A (en) * | 1954-06-08 | 1960-04-12 | California Research Corp | Process of catalytic desulfurization and hydrocracking of hydrocarbons followed by catalytic cracking |
US2924568A (en) * | 1955-02-28 | 1960-02-09 | Exxon Research Engineering Co | Process for hydrodesulfurizing and subsequently catalytically cracking gas oil |
US2945803A (en) * | 1958-04-14 | 1960-07-19 | Gulf Research Development Co | Process for hydrogen treatment and catalytic cracking of petroleum hydrocarbons |
US4115527A (en) * | 1969-03-31 | 1978-09-19 | Kureha Kagaku Kogyo Kabushiki Kaisha | Production of carbon fibers having high anisotropy |
US3654130A (en) * | 1969-11-10 | 1972-04-04 | Exxon Research Engineering Co | Preparation of high v.i. lube oils |
BE759139A (en) * | 1970-02-20 | 1971-04-30 | Mitsubishi Oil Co | PROCESS FOR MANUFACTURING A CARBON FIBER |
US3671419A (en) * | 1970-02-27 | 1972-06-20 | Mobil Oil Corp | Upgrading of crude oil by combination processing |
US3928170A (en) * | 1971-04-01 | 1975-12-23 | Kureha Chemical Ind Co Ltd | Method for manufacturing petroleum pitch having high aromaticity |
US3948756A (en) * | 1971-08-19 | 1976-04-06 | Hydrocarbon Research, Inc. | Pentane insoluble asphaltene removal |
CA1019919A (en) * | 1972-03-30 | 1977-11-01 | Leonard S. Singer | High modulus, high strength carbon fibers produced from mesophase pitch |
US4005183A (en) * | 1972-03-30 | 1977-01-25 | Union Carbide Corporation | High modulus, high strength carbon fibers produced from mesophase pitch |
US3974264A (en) * | 1973-12-11 | 1976-08-10 | Union Carbide Corporation | Process for producing carbon fibers from mesophase pitch |
US3976729A (en) * | 1973-12-11 | 1976-08-24 | Union Carbide Corporation | Process for producing carbon fibers from mesophase pitch |
US4026788A (en) * | 1973-12-11 | 1977-05-31 | Union Carbide Corporation | Process for producing mesophase pitch |
NL7507484A (en) * | 1975-06-23 | 1976-12-27 | Shell Int Research | PROCESS FOR CONVERTING HYDROCARBONS. |
US4048057A (en) * | 1976-10-04 | 1977-09-13 | Pullman Incorporated | Integrated heavy oil cracking process utilizing catalyst separated from cracking in pretreating zone |
JPS53119917A (en) * | 1977-03-29 | 1978-10-19 | Koa Oil Co Ltd | Manufacture of high aromatic pitch from petroleum heavy oil |
JPS54160427A (en) * | 1977-07-08 | 1979-12-19 | Exxon Research Engineering Co | Production of optically anisotropic* deformable pitch* optical anisotropic pitch* and pitch fiber |
US4219404A (en) * | 1979-06-14 | 1980-08-26 | Exxon Research & Engineering Co. | Vacuum or steam stripping aromatic oils from petroleum pitch |
JPS5627611A (en) * | 1979-08-13 | 1981-03-18 | Miwa Denki Kk | Measuring instrument with fingers |
US4271006A (en) * | 1980-04-23 | 1981-06-02 | Exxon Research And Engineering Company | Process for production of carbon artifact precursor |
JPS5788016A (en) * | 1980-11-19 | 1982-06-01 | Toa Nenryo Kogyo Kk | Optically anisotropic carbonaceous pitch for carbon material, its manufacture, and manufacture of carbonaceous pitch fiber and carbon fiber |
JPS5930192B2 (en) * | 1980-12-15 | 1984-07-25 | 富士スタンダ−ドリサ−チ株式会社 | Potential anisotropic pitch |
US4521294A (en) * | 1981-04-13 | 1985-06-04 | Nippon Oil Co., Ltd. | Starting pitches for carbon fibers |
JPS57168988A (en) * | 1981-04-13 | 1982-10-18 | Nippon Oil Co Ltd | Raw pitch for carbon fiber |
JPS57179286A (en) * | 1981-04-27 | 1982-11-04 | Nippon Oil Co Ltd | Raw material pitch for carbon fiber |
-
1981
- 1981-08-18 JP JP56128141A patent/JPS5829885A/en active Granted
-
1982
- 1982-08-18 US US06/409,216 patent/US4462894A/en not_active Expired - Fee Related
- 1982-08-18 DE DE8282107538T patent/DE3272453D1/en not_active Expired
- 1982-08-18 EP EP82107538A patent/EP0072573B1/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2992181A (en) * | 1957-09-11 | 1961-07-11 | Sinclair Refining Co | Process for producing a petroleum base pitch |
DE1966045A1 (en) * | 1968-04-04 | 1971-05-19 | Kureha Chemical Ind Co Ltd | Resinous pitch compositions |
DE2006524A1 (en) * | 1969-02-13 | 1970-08-27 | Kureha Kagaku Kogyo Kabushiki Kaisha, Tokio | Process for rendering pitch parts infusible |
US4086156A (en) * | 1974-12-13 | 1978-04-25 | Exxon Research & Engineering Co. | Pitch bonded carbon electrode |
FR2412606A1 (en) * | 1977-12-21 | 1979-07-20 | Standard Oil Co | PROCESS FOR CRACKING HEAVY HYDROCARBON CURRENTS |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0084776A2 (en) * | 1982-01-13 | 1983-08-03 | Mitsubishi Oil Company, Limited | Process for producing pitch for using as raw material for carbon fibers |
EP0084776A3 (en) * | 1982-01-13 | 1983-08-31 | Mitsubishi Oil Company, Limited | Process for producing pitch for using as raw material for carbon fibers |
EP0117099A2 (en) * | 1983-02-08 | 1984-08-29 | Fuji Standard Research Inc. | Novel carbonaceous pitch, process for the preparation thereof and use thereof to make carbon fibers |
EP0117099A3 (en) * | 1983-02-08 | 1985-04-17 | Fuji Standard Research Inc. | Novel carbonaceous pitch, process for the preparation thereof and use thereof to make carbon fibers |
Also Published As
Publication number | Publication date |
---|---|
US4462894A (en) | 1984-07-31 |
DE3272453D1 (en) | 1986-09-11 |
EP0072573B1 (en) | 1986-08-06 |
JPS61876B2 (en) | 1986-01-11 |
JPS5829885A (en) | 1983-02-22 |
EP0072573A3 (en) | 1983-04-13 |
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